Roberts, Caserio - Basic Principles of Organic Chemistry (2nd edition, 1977)

from reduction, of nitro compounds, 1151 resonance in, and base strengths of, 11131115 ring substitution reactions of, 1128-1 129

from Schmidt degradation, 1153, 1156 N-substituted, rearrangements of, 1139-1 140

Arene polyols, 13031305

Arenediazonium salts (see Benzenediazonium salts)

Arenes (see also Benzene, Methylbenzene, Naphthalene, etc.), acid strengths of alkyl (table), 1322

alkyl substituted, from coal tar and petroleum, 1079-1081

from arenediazonium salts, 1134, 1138 charge-transfer complexes of, 11921193

in chlorination of alkanes, selectivity effects, 102 from coal tar, 1079-1083

cycloaddition reactions of, 1077

electronic spectra of, benzene chromophore and, 1030-1034

benzenoid band in, 10321033 halides from, 10441046 halogen addition to, 1076

and Hammett equation, 1329-1337 hydrogen exchange of, 1057 hydrogenation of, 414

infrared spectra of, 276, 1027-1029

IUPAC rules of nomenclature for, 1024-1026 ketones from, 1051-1053

nitration of, 1041-1043, 1058-1072, 1187-1190 nrnr spectra of, ring currents and, 1034-1035

spin-spin splittings in, 1036-1037 nomenclature of, 62-64

oxidation of, with oxygen and vanadium catalysts, 1077-1078

from petroleum by catalytic reforming, 1079-1081

physical properties of (table), 1026-1027 picrates of, 1192

proton chemical shifts of, 311 reactivity correlations of, 13291337

reduction of, Birch procedure for, 10741075 by hydrogenation, 10221024

with sodium in alcohol, 1073-1074 side-chain derivatives of, 1316-1328 side-chain halogenation of, 546-547, 1046,

1317-1318

side-chain substituted, 1287, 1327-1328 spectral properties of, 10271036 toxicity of, 1026

Arenols {see also Phenols), properties of (table), 1288-1291

Arginine, properties, 1209 Arndt-Eistert synthesis, 1200

Aromatic character, and benzene, 10, 173-174, 957-968

of dibenzenechromium, 1507 of ferrocene, 15041507

of nonbenzenoid cyclic polyenes, 981-995, 1084-1089, 1090

Aromatic halides (see Aryl halides)

Aromatic hydrocarbons, production and uses of (tables), 1079-1083

Aromatic substitution (see Electrophilic or Nucleophilic aromatic substitution)

Aryl azides, from arenediazonium salts, 1139 Aryl ethers, cleavage of, 1295

preparation of, 1294

Aryl halides, from arene halogenations, 1039, 10441046, 10701072

from arenols, 1295

from benzenediazonium salts, 1134-1 136 benzyne from, 1120

nitriles from, 11841185

nucleophilic substitution of, radical mechanism for, 573

organomagnesium compounds from, 576-577 organometallic compounds from, by

halogen-metal exchange, 574 with metals, 572-573

physical properties of (table), 537-538 preparation of (table), 551-552, 589 uses of, 561

Aryl nitro compounds (see Nitrobenzene) Arylmethanes, acid strengths of (table), 1322 Arynes (see also Benzyne), from aryl halides,

558-559 Ascaridole, 1466

L-Ascorbic acid, properties of, 650 structure of, 938

Asparagine, codon for, 1282 hydrolysis of, 1229 properties, 1209

Aspartic acid, ionization equilibria of, 1214 properties, 1209

Asphalt, 74 Aspirin, 1328

Asymmetric synthesis, in aldol addition, 893-894 in biological reactions, 894

principles of, 893-894 Atactic polymers, 1430-1435 Atomic energy states, 268-269

Atomic-orbital models, ab initio calculations with, 179-182

of alkanes, 162

alkyne-alkane acidity and, 439-440 for benzene, 172175, 967-968

of carbonyl bonds, 675 of E2 transition state, 247 of ethane, 162

of ethene, 165-167 of ethyne, 167-168 of hydrogen, 962-963 of methanol, 164-165

for methide anion, 169

for methyl carbocation, 169 for methyl radical, 169170 of 1,2-propadiene, 508-509

for 2-propenyl radical, 178-178

for S, transition states of, 221, 223

Atomic orbitals, bond formation with, 155157, 960-966

for carbon, 154-155 designations for, 151-152 electron pairing in, 153154

electron probabilities and, 151-152 energies of, 151-153

ground-state electronic configurations of, 153-155

hybrid, sp-type, 159, 167-168 sp2-type, 160-161, 165-166 sp3-type, 160, 162

hybridization of, 159161 hydrogenlike, 151-152 order of filling, 153-155

overlap of, in bond formation, 155-161, 962-966 and bond strengths, 159-160

phases of, 156

pi (T)overlap, 165-167

promotion of electrons in, 158-160, 163-164 quantum numbers of, 151-152

shapes of, 151-152

sigma (o) overlap, 156-165 tau (7) bonds with, 165-167

for unshared electrons, 162-165, 168-172 valence state configurations, 158-160, 163, 168

Atomic weights, determination of, 4 ATP (see Adenosine phosphate esters) Atropine, 1097

Autoxidation, of benzenecarbaldehyde, 712-7 13 of ethers, 658-659

of (1-methylethyl)benzene, 721 Autumn crocus, 1316 Auxochromes, definition of, 1030

substituent effects of, 1402-1404 Avogadro, A., 4

Axial positions (see Cyclohexane) Azabenzene, in alkyl halide formation, 627

base strength of, 1117-1 118 from coal tar, 1080

physical properties of, 239, 1101 stabilization energy of, 985

in sulfonate ester formation, 629 Azabenzene-chromic acid, alcohol oxidation

with, 642

Azacycloalkanes, nomenclature systems for, 659-66 1

1-Aza-2-cycloheptanone,from cyclohexanone oxime, 1181

polymer from, 1181, 1433, 1441 Azacyclohexane, physical properties of, 1101 Azacyclohexanes, inversion rates of, 1110 Aza-2,4-cyclopentadienes, from

1,4-alkanediones, 778

1-Aza-2-cyclopentanone,solvent properties of, 1168

Azacyclopropanes, inversion rates of, 1110 1-Azanaphthalene, base strength of, 1118

from coal tar, 1080

Azane oxides (see also Amine oxides), 1143 Azanols, in arnine oxidations, 11431144

Azanyl hydrogen sulfate, organoborane reactions, 427, 430-43 1

Azarenes, base strengths of, 11171118

from diarylethanediones, 1326 Azeotropes, definition of, 258 Azides, from alkyl halides, 1202

m i n e s from, 1146, 1148, 1150, 1153, 1156, 1202 from arenediazonium salts, 1139

explosive properties of, 1202 from hydrazines, 1197, 1202 reduction of, 1202

Azine (see Azabenzene) Azine dyes, 1406

Azines, from aldehydes and ketones, 698 Azlactones, from amino acids, 1222

Azo compounds, from arenediazonium couplings, 1137

from hydrazines, 1197

initiation of polymerization with, 1447 preparation of, 1194, 1198

radical decomposition of, 1198 Azobenzene, as dye component, 1407

preparation of, 1194 reduction of, 1194

thermal decomposition of, 1198 Azobisisobutyronitrile, initiation of polymerization

with, 1447 Azomethine dyes, 1414 Azonia nomenclature, 1102

Azoxybenzene, from nitrobenzene, 1194 Azulene, basicity of, 1085

polarity of, 1084 rearrangement of, 1084 stabilization energy of, 985 substitution reactions of, 1084

Bachmann, W. E., and equilenin synthesis, 1495 Back bonding, 1509-15 10

Back-side approach, 219-223 Bactericides, aryl halides for, 561

Baeyer, A., and strain in cycloalkanes, 463-465 Baeyer-Villiger oxidation, of aldehydes and

ketones, 712-713 Bakelite resins, 1442-1443

Ball-and-stick models, of carbon compounds, 34-35

of cis-trans isomers, 112114

of conformations, 122-123, 449-452 Paterno and, 3

Bartlett, P. D., and carbocation hydrogen-transfer reactions, 397-398

Barton, D. H. R., and conformational analysis, 124, 450

Base catalysis, of aldehyde and ketone halogenations, 742-745

of aldol additions, 749-754

of aldose-ketose interconversions, 918-9 19 of chiral ketone racemization, 896

of dehydration of aldols, 755-756 of en01 and keto equilibria, 828

of enolization, 736-738

of hydrogen cyanide to aldehydes and ketones, 689-690

of nitrile hydrolysis, 1178

of unsaturated alkanoic acid rearrangements, 841 Base strengths, standard expressions for, 1111-1 112 Bay, oil of, 1462, 1464

9-BBN, from 1,5-cyclooctadiene, 423 Beckmann rearrangement, amides from, 1149,

1153, 1180-1181 arnines from, 1149, 1153 Beer-Lambert law, 291, 293

Benadryl, 1328

Benzal chloride (see Dichloromethylbenzene) Benzal fluoride (see Difluoromethylbenzene) Benzaldehyde (see Benzenecarbaldehyde)

Benzedrine, 1098

Benzenamine, from aryl halides, 557-558, 1128

Hammett correlation of, 1334 1,4-benzenedione from, 1145 bromination of, 1128

from bromobenzene, 557-558

electronic absorptions of, 10301033, 14021403 hydrogenation of, 1073

from nitrobenzene, 1193 oxidation of, 11441145 physical properties of, 1101 stabilization energy of, 986

substituted, basicities of (table), 1114-1 116 Benzenamines, from aryl halides, 557-558, 1128 Benzene, acylation of, 1051-1053

alkyl substituted, nitration of, 1042-1043 alkylation of, 10471050

atomic-orbital model of, 172-1 74, 968-969 benzenol from, 12911293

Birch reduction of, 10741075 bond lengths in, 987 bromination of, 1044-1045 bromine addition to, 967-968

bromine substitution of, 552, 1044-1045 charge-transfer complexes of, 1192-1 193 chlorine addition to, 1076 chlorobenzene from, 1291 chloromethylation of, 1054, 1319 chlorosulfonation of, 1056

chromium derivative of, 15061507 as chromophore, 1402 1,4-cyclohexadiene from, 10741075 delocalization energy of, 173176

derivatives of, IUPAC rules of nomenclature for, 10241026

spectral properties of, 1027-1037 deuterated, preparation of, 1057

Dewar resonance structures for, 175-176 electrophilic substitutions of (table), 10371040 fluorescence and phosphorescence of, 1375 Friedel-Crafts alkylation of, 10471050 general reactions of, 967-968

geometry of, 173, 966 GVB treatment of, 983-984

halogen additions to, 1046

heat of combustion of, 174, 967 heat of hydrogenation of, 967 hexachloride of, 1066

and 1,3,5-hexatriene, 967-968 hydrogen exchange of, 1057 hydrogenation of, 967-968, 10721073 industrial syntheses based on, 1082 iodination of, 1044-1045

Kekuli: and, 10

ketones from by acylation, 10511053 mercuration of, 1058

molecular-orbital treatment of, 969-97 1 nitration of, 1041

with nitric acid, 967-968 nomenclature of, 62-64

oxidation of, with oxygen and vanadium catalysts, 10771078

with ozone, 967-968, 1078 from petroleum, 10791083 photoelectron spectra of, 1357 physical properties of, 239, 1027 radical anion of, 1075 representations of, 974

resonance treatment of, 173-177, 972-974 sandwich compound of, 15061507 stability of, 173-175

stabilization energy of, 967-968, 985 structure of, 1011, 966-967

structure problem presented by, 9- 11 substituted, orientation effects in, 1058-1068 substituting agents for, 1037-1058 sulfonation of, 1055-1057

with tetracyanoethene, 968 valence-bond treatment of, 972-975

Benzenecarbaldehyde, aldol addition of, with 2-propanone, 756

autoxidation of, 712-713 benzoin from, 1324

from chloromethylbenzene, 1318 from dichloromethylbenzene, 1318 difluoromethylbenzene from, 1318 electronic absorptions of, 10301031 glycosides of, 926, 1327

Hammett reactivity correlations with, 1334 physical properties of, 679

with sulfur tetrafluoride, 1318 Benzenecarboxylic acid, from oxidation of

methylbenzene, 1317 physical properties of, 792

substituted, acidities of (table), 1327-1333 from trichloromethylbenzene, 1318

1,4-Benzenediamine,arenecarboxamide polymers from, 1456-1457

base strength of, 1115

ladder polymers from, 14561457 from phenyldiazane, 1140

l,2-Benzenediarnines, quinoxalines from, 1326

1,4-Benzenediamines, as color developers,

1413-1414

Benzenediazonium salts, aryl azides from, 1138 azo compounds from, 1137

copper catalysis of reactions of, 1134-1136 coupling to biaryls, 1138

coupling with alkenes, 1135-1 136 cyanoarenes from, 1134 decomposition of, 1133

diazo coupling of, 11371138 diazotate salts from, 1139 hydrazines from, 1138

with hypophosphorous acid, 11891190 iodide reaction with, 1136

with I-naphthalenol, 1300 nitriles from, 1185

nitro compounds from, 1191 phenyl cations from, 1133, 1135 phenyl radicals from, 11351136 preparation of, 1133

reactions of (table), 1138-1 139 reduction of, 1134, 1138, 11891190 triazenes from, 1137

1,2-Benzenedicarbonitrile,copper phthalocyanine from, 1408

1,2-Benzenedicarboxyhydrazide,1127

1,2-Benzenedicarboximide,acidity of, 1176 hydrazine cleavage of, 1127

hydrolysis of, 1127

in Gabriel m i n e synthesis, 1127 synthesis of, 850

1,2-Benzenedicarboxylicacid, anhydride from, 847 properties and uses of, 849

1,3-Benzenedicarboxylicacid, polyesters from, 1440

1,4-Benzenedicarboxylicacid, 1,4-di- (trifluoromethyl) benzene from, 1318

epoxy resins from, 1444-1445 polyesters from, 1438

polymers from, 1433, 1456I457 properties and uses of, 849

with sulfur tetrafluoride, 1318 1,2-Benzenedicarboxylicanhydride, from

naphthalene oxidation, 1078 polyesters from, 1439-1441

uses of, 1078

1,2-Benzenediol, 1,2-benzenedione from, 1303 from 1,2-dichlorobenzene, 1303

physical properties of, 1289 1,3-Benzenediol, from 1,3-benzenedisulfonic

acid, 1304

physical properties of, 1289 1,4-Benzenediol, 1,4-benzenedione from, 1303

from 1,4-benzenedione, 13061307 electrode potential of, 1306

as photographic developer, 1310-13 11 physical properties of, 1289

as polymerization inhibitor, 1449

substituted, from 1,4-benzenedione additions, 1311-13 12

1,2-Benzenedione, from 1,2-benzenediol, 1303 as quinone, 1305

1,4-Benzenedione, additions to, of

1,3-butadiene, 1312

of ethanoic anhydride, 1311-1312 of hydrogen chloride, 1311-13 12

from benzenamine, 1145, 1303

Index

from 1,4-benzenediol, 1303 1,4-benzenediol from, 1303 from benzenol, 13001301

complex with 1,4-benzenediol, 1307 electrode potential of, 1306

with hydroquinone, 1307

in photographic development, 1311 quinhydrone from, 1307

reduction of, 13061308 semiquinone from, 1307

1,3-Benzenedisulfonicacid, 1,3-benzenediol from, 1304

Benzenesulfonic acid, from benzene, 1055, 1291 benzenol from, 1291

preparation of, 1055-1056

Benzenesulfonyl chloride, m i n e protecting groups from, 1161

benzenesulfonic acid from, 1056 in Hinsberg test for arnines, 1123 preparation of, 1056 sulfonamides from, 11221123 sulfonate esters from, 629

1,2,4,5-Benzenetetracarboxylicacid, ladder polymers from, 1456

polyimides from, 1456

1,2,4,5-Benzenetetracarboxylicdianhydride, polyesters from, 1440

1,2,3-Benzenetriol,from

2,3,4-trihydroxybenzenecarboxylicacid, 1304

1,2,5-Benzenetriol, ethanoate ester, 1312

1,3,5-Benzenetriol, from

2,4,6-trinitrobenzenecarboxylicacid, 1304 Benzenol, acidity of (table), 736-738, 1293-1294

aldol type reactions of, 1300 Bakelite resins from, 14421443 from benzene, 1291-1292

from benzenediazonium salts, 1133, 1136 14-benzenedione from, 13001301

from benzenesulfonic acid, 1291 bromination of, 12961297 carboxylation of, 12971298 from chlorobenzene, 557, 1291 from coal tar, 1081, 1291

with diazomethane, 1294 with dichlorocarbene, 1299

electronic absorptions of, 10301032, 14021403 as enol, 651

esters from, 1294 ethers from, 1294 hydrogenation of, 1073

from hydroperoxide rearrangement, 721-722 2-hydroxybenzenecarbaldehyde from, 1299 2-hydroxybenzenecarboxylic acid from,

12981299

from isopropylbenzene, 1293

IUPAC rules of nomenclature for, 191 Kolbe-Schmitt reaction of, 1298-1299 with methanal, 1300, 1442-1443

from methylbenzene, 12921293 oxidation to quinone, 13001301 physical properties of, 1289, 1291 quinone from, 1300-1301

radical from, 1301

sodium salt, electronic absorptions of, 1032 stabilization energy of, 986, 1293

Benzhydrol (see Diphenylmethanol) Benzhydryl derivatives (see Diphenylmethyl

derivatives)

Benzidine, as carcinogen, 1162 from hydrazobenzene, 1140 rearrangement of, 1140

Benzil, as 1,2-dione, 774-775 formation of, 1325 quinoxalines from, 1326

rearrangement of, 775, 1325-1326

Benzilic acid rearrangement, of diarylethanediones, 775, 1326

Benzocaine, 1328

Benzoic acid (see Benzenecarboxylic acid) Benzoin, formation of, 1324-1325

oxidation to benzil, 1325 Benzoin condensation, 13241325

Benzophenone (see Diphenylmethanone) Benzopinacol, 13821383

Benzoquinone (see 1,4-Benzenediol) Benzotrichloride (see Trichloromethylbenzene) Benzotrifluoride (see Trifluoromethylbenzene) Benzoyl chloride (see Benzenecarbonyl chloride) Benzoyl nitrate, 1043

Benzoyl peroxide, initiation of polymerization with, 1447

Benzyl alcohol (see Phenylmethanol) Benzyl bromide (see Bromomethylbenzene) Benzyl chloride (see Chloromethylbenzene) Benzyl halides (see Phenylmethyl halides)

Benzyloxycarbonyl groups, as protecting group for mines, 11591160, 12371239

Benzylpenicillin (see Penicillin G)

Benzyne, from amine salts, with aryl halides, 1120 from 2-benzenediazoniumcarboxylate,559 cycloadditions of, 559

1,3-cyclopentadiene addition, 576

as intermediate in aryl halide reactions, 557-559 nucleophilic additions to, 558-559

from organometallic reactions, 575 Bercaw, J. E., and nitrogen fixation by

zirconocene, 1508 Bergamot, oil of, 1468

Bernal, J. D., and structures of steroids, 1476-1477 Beryllium hydride, bonding in, 157159

properties of, 19 BHC, 1076 Biacetyl, 774

Biaryls, from arenediazonium salt couplings, 1138 chiral forms of, 510-5 11

Bicyclo[l.l.O]butane, from 1,3-butadiene, 1389 physical properties and strain energy of

(table), 483 Bicyclo[4.4.0]decane (see Decalin)

Bicyclo[2.2.1]-2,4-heptadiene(see Norbornadiene) Bicyclot2.2.llheptane, exo-endo isomerism of

derivatives of, 497 synthesis of, 526-527

Bile acids, 14751477

Bimolecular reactions, 216 Bioluminescence, 13971399 Biosynthesis, of alkaloids, 1489

of aromatic rings, 1481-1482 of cephalosporins, 1492

of cholesterol, 1486-1488 of fatty acids, 1480-1481 of penicillins, 1492

of prostaglandins, 14931494 of terpenes, 1483-1485

Biotin, in fatty acid synthesis, 1483 Biphenyl, electronic absoprtions of, 1031

from Grignard coupling, 1505 quinone of, 1306

stabilization energy of, 985 4,4'-Biphenyldione, as quinone, 1306 Biphenylene, stabilization energy of, 985 Biphenyls, chiral forms of, 510-5 11

Biradical intermediates, in [2+21 cycloadditions, 1014-1017

Birch, A. J., and acetogenin hypothesis, 1481-1482 and reduction of arenes, 1074-1075

Bisabolene, 1468 Bis(cyclooctatetraene)uranium, 1508 Bis(pentenylnickel), 1508

Bisphenol A, epoxy resins from, 14441445 polyesters from, 1439

Bisulfate (see Hydrogen sulfate) Bisulfite (see Hydrogen sulfite)

Bloch, K., and fatty acid biosynthesis, 1480 Block polymers, 1452, 1454-1455

Bohr frequency condition, 269 Bombykol, structure and activity of, 141

in carbocylic rings, 448, 462-465, 484

and electronic repulsions, 157-164, 169-172 Bond energies (see also Bond-dissociation

energies), accuracy of, 79-80, 465 average values of, 78-80

and chlorination of methane, 85 of cycloalkanes, 465

definition of, 76-79 and reactivity, 96-97

resonance effect on, 177-178 tables of, 77, 92, 674

Bond formation, with atomic orbitals, 155157 by pi (n) overlap, 165-167

by sigma (o) overlap, 156-165

Bond lengths, and bond energies, 960-961 of carbon-carbon bonds, 36-37

of carbon-chlorine bonds, 37 of carbon-hydrogen bonds, 37 and double-bond character, 987

and hybridization (table), 987-988

Bond strengths, correlation with leaving group reactivity, 232-233

Bond-dissociation energies, definition of, 93 table of, 92

Borane, reduction of carbonyl compounds with (table), 707-708

Borane reductions, alcohols from, 610

Boranes, additions to alkenes, 380, 420-429 carbonylation of, 724-726

oxidation of, 427-43 1

Boron hydrides (see Hydroboration) Boron trifluoride, ether complexes of, 656

Bragg, W. and L., and x-ray diffraction structure determinations, 1249

Bredt's rule, and polycycloalkenes, 484 Bridgehead double bonds, Bredt's rule and, 484 Bright scarlet, 1407

Bromination, of alkanes, selectivity in, 101-102 of arenes, 1044-1045, 1070-1072

of hydrocarbons, with N-bromobutanimide, 103-104

Bromine, addition to ethyne, 382 additions to alkenes, 360-367, 379

aluminum bromide catalysis of addition of, 16 azide of, addition to alkenes, 379 radical-chain addition to alkenes and

alkynes, 389

N-Bromoamides, in Hofmann degradation, 1155-1 156

Bromobenzene, amination of, 557-558 from benzene and bromine, 552 physical properties of, 538

N-Bromobutanimide (NBS, N-bromosuccinimide), in additions to alkenes, 379

allylic bromination of alkenes with, 542-543 bromination of hydrocarbons with, 103-104 and hydrogen fluoride, in additions to

alkenes, 379

with methylbenzene, 1317 Bromocyclohexane, conformational equilibria

of, 454, 457 Bromoethane, hydrolysis of, 12

structure of, 3-6 Bromoform, 746

Bromomethane, electronic spectrum of, 289 SN2reactivity and nucleophile structure

(table), 235

(Bromomethyl)benzene, from methylbenzene and tert-butyl hypobromite, 106

from methylbenzene and bromotrichloromethane, 104

l-Bromo-2-methylpropane, from hydrogen bromide and 2-methylpropene, 374-376

2-Bromo-2-methylpropane, from hydrogen bromide and 2-methylpropene, 374-376

Bromonium ions, in bromine additions to alkenes, 365-366

from l-bromo-2-fluoroethane, 366 l-Bromo-2-phenyl-l-propene, photochemical

isomerization of cis-trans isomers of, 1386 2-Bromopropane, E2 reaction of, 241

SN2reaction of, 241 3-Bromopropene, from propene and

N-bromobutanimide, 104 N-Bromosuccinimide (see N-Bromobutanimide) Bromotrichloromethane, radical-chain addition to

alkenes and alkynes, 389

Br$nsted, J. N., and acid-base theory, 208

Brown, C., 5

Brown, H. C., and hydroboration, 421 Brucine, 867, 1097

Bucherer reaction, 1295-1296 Bullvalene, 10891090

Burgstahler, A. W., and cantharidin synthesis, 1497-1498

1,3-Butadiene, with l,4-benzenedione, 1312 bond distances in, 37

bromine addition by 1,2 and 1,4 modes, 489 chlorine addition to, 1441

cis-trans isomers of polymer of, 505 copolymerization of, with ethenylbenzene

(styrene), 506

with propenenitrile (acrylonitrile), 506 [4+41 cycloaddition of, 1004 dimerization of, 1004

electrocyclic reactions of, 1005-10 14 electronic spectrum of, molecular-orbital

treatment of, 980-98 1 transitions of, 289-29 1

ethene addition to, 492

heat of hydrogenation of, 415 1,6-hexanediaminefrom, 1441 homopolymerization of, 504-505 hydrogen bromide addition to, by radical

mechanism, 491

hydrogen chloride addition to, by 1,2 and 1,4 modes, 490, 542

iron tricarbonyl complex of, 1523 molecular-orbital treatment of, 475-477 molecular orbitals of, 976

nickel complexes of, 1523

photochemical additions and cycloadditions of, 1388

photochemical reactions of, 13881389 rotational conformations of, 495 s-cis-trans isomers of, 495

stabilization energy of, 986

sulfur dioxide cycloadduct, 500-501 tetrduoroethene cycloadducts of, 502, 1014-1017 valence-bond treatment of, 977

1,3-Butadiyne, from oxidative coupling of ethyne, 441

Butanal, electronic absorption of, 795

by hydroformylation of propene, 722-723 physical properties of, 679

Butane, bond distances in, 37 conformational energies of, 123-125 conformations of, 123125

heat of combustion of, 79 rotational barrier of, 123-124

Butanedioic acid, anhydride from, 847 in citric acid cycle, 951-954 properties and uses of, 847

Butanedioic anhydride, polyesters from, 1440 2,3-Butanedione, from photolysis of

2-propanone, 1379 physical properties of, 679 Butanimide, acidity of, 850-85 1

N-bromo derivative of (see N-Bromobutanimide)

Index

resonance in, 850-85 1 synthesis of, 850

Butanoic acid, electronic absorption of, 795 physical properties of, 792

I-Butanol, industrial preparation of, 759 2-Butanone, alkylation of, 763

halogenation of, 745 infrared spectrum of, 273 mass spectrum of, 340-341 physical properties of, 679

2-Butenal, physical properties of, 679 preparation of, 755-756

1-Butene, heat of hydrogenation of, 415 infrared spectrum of, 353

2-Butene, allylic chlorination of, 543 bond distances in, 37

cis-, heat of hydrogenation of, 415 cis-trans isomers of, 111-1 12

from ethene, by metathesis, 1520-152 1 trans-, heat of hydrogenation of, 415

cis-Butenedioic acid, anhydride from, 847 properties and uses of, 849

trans-Butenedioic (fumaric) acid, biological hydration of, 371-372

in citric acid cycle, 951-954 properties and uses of, 849

Butenedioic anhydride, from benzene oxidation, 1077-1078

copolymerization of, 1452 as dienophile, 496-498, 1077 in fiberglass, 1440

naphthalene addition of, 1077 polyesters from, 1440

3-Buten-Zone, electronic spectrum of, 289 in Robinson annelation, 1477-1478

1-Buten-3-yne(vinylacetylene), bond distances in, 37

from dimerization of ethyne, 441 nmr spectrum of, 1353

tert-Butoxycarbonylprotecting groups, in peptide syntheses, 12371247

Butter Yellow, as carcinogen, 1162 from diazo coupling, 1137

Butyl alcohol

tert-Butyl alcohol (see 2-Methyl-2-propanol) Butyl Carbitol, 656

tert-Butyl hypobromite, bromination of hydrocarbons with, 106

tert-Butyl hypochlorite, in additions of alkenes, 379 for hydrocarbon chlorinations, 103104

with methylbenzene, 1317 Butyl rubber, 506, 508, 1432

N-tert-Butylalkanamides,from Ritter reaction, 1178-1 179

tert-Butylcyclohexane, conformational equilibria of derivatives of, 458-460

tert-Butylhydroperoxide, alkylzirconocenes oxidation with, 1514

2-Butyne, bond distances in, 37 hydrogenation of, 413-4 14 Butyric acid (see Butanoic acid)

C-alkylation, of enolate anions, 762-763 of ester anions, 833-835

of phenols, solvent effect on, 1297-1298 C-carboxylation, in Kolbe-Schmitt reaction, 1299

of ribulose, 941-942

Cadmium alkyls, ketones from, with acyl halides, 731

Caffeine, 1097

Cahn-Ingold-Prelog convention for configurations, 879-884

Calvin, M., and path of carbon in photosynthesis, 941-943

Camphene, 1464

Camphor, as isoprenoid, 14661467 synthesis of, 1467

Cancer chemotherapy, 1163 Cane sugar (see Sucrose) Cannabinols, 1305

Cannizzaro, S., aldehyde oxidation-reduction reaction of, 707-709

and atomic weights, 4

Cannizzaro reaction, of ethanedial, 775 Cantharidin, synthesis of, 1497 Caprolactam (see I-Aza-2-cyclopentanone)

Carbamic acids, from tert-butoxycarbonyl group hydrolysis, 1160

from isocyanates, 11551156 polyurethane foams and, 1455

Carbanions (see also Enolate anions), bonding and geometry of, 169

C- vs. 0-alkylation of, 762-763, 833-835, 1297-1298

sulfur, nitrogen, and phosphorus stabilized, reactions of, 691-693, 765-767

Carbazole, from coal tar, 1080

Carbene, carbon-hydrogen insertion of, 1200 from diazomethane, 1200

dichlorofrom trichloromethane, formation and reactions of, 563-564

Carbenes, complexes with transition metals, 1512, 1520-1521

cyclopropanes and cyclopropenes from, 565 electronic structure of, 564

formation of (table), 563-566 reactions and reactivity of, 563-567 rearrangement of, 567

singlet and triplet, 564

in tetrduoroethene preparation, 568 Carbenium ions (see Carbocations) Carbitols, 656

Carbocations, in alcohol dehydrations, 631-633 in alkene hydrations, 368-37 1

from alkyldiazonium salts, 1130-1 131 in arene alkylations, 10471050

aryl, from arenediazonium salts, 1133-1 136 atomic-orbital model of, 223

bonding and geometry of, 169

in halide formation, from alcohols, 626 in halogen additions to alkenes, 361-367 hydrogen-transfer reactions with alkanes,

397-398

hyperconjugation and, 228

methyl groups and stability of, 375 rearrangement of, in alcohol dehydrations,

632-633

relative rates of, 25 1

stability order of, 226-228 stereochemistry of, 222-223 steric hindrance and, 229

in terpene and steroid biosynthesis, 1484-1489 thermochemistry of formation of, 212-2 13 tropylium ion and, 1315

Carbohydrates, classification of (table), 902-908 definition of, 902

determination of configurations of, 909-9 12 enzymatic hydrolysis of, 930

furanose ring in, 920-922

hemiacetal and hemiketal structures of, 903-906 Kiliani-Fischer cyanohydrin synthesis of, 911 metabolism of, 944-956

nomenclature of, 903-908 occurrence of (table), 907-908 from photosynthesis, 939-943

physical properties of (table), 907-908 properties of, 909

pyranose ring in, 920-922 ring sizes in, 920

Wohl degradation of, 910

Carbon, bonding of, 18-19, 30-34, 162-168, 179-182, 964-968

oxidation states of, 405-409 tetrahedral, 6-7, 34-36, 160-161 valence of, 4-5, 34-36, 160, 405-409

Carbon-carbon bond formation, reactions for (table), 518

Carbon-carbon bonds, lengths of (table), 36-37 Carbon-chlorine bonds, lengths of (table), 37 Carbon dioxide, equilibration with water, carbonic

anhydrase for, 1260

fixation in photosynthesis, 939-943

with organometallic compounds, 570-57 1, 579, 583

with phenols, 1298-1299

Carbon disulfide, physical properties of, 239 Carbon-hydrogen bonds, lengths of (table), 37 Carbon monoxide, with alkylzirconocenes, 1514

with arenes in Gattermann-Koch synthesis, 1053 copolymer with ethene, 1453

with di-n-propenylnickel, 1522

in hydroformylation, 722-723, 15181519 insertion reactions of, 1512, 1514, 1516, 1518 methanol from, by hydrogenation, 612

from photolysis of 2-propanone, 1379

with transition-metal compounds, 15121516, 1518-1520, 1522-1524

Carbonate esters, amides from, 11771178 Carbonate ion, and resonance, 176177 Carbonic anhydrase, 1260

Carbonium ions (see Carbocations)

Carbonyl bond, alkene bond comparision, 673-674

Index

atomic-orbital model, 675 dipole moment, 674-675 energies (table), 674 hydration of, 673-674 polarity of, 674-678

Carbonyl compounds (see Aldehydes, Ketones, Carboxylic acids, and so on)

Carbonyl group, addition reactions to, 577-586, 685-7 12

electronic spectra of, 681 genera1 characteristics of, 671-678

infrared properties of (table), 680-68 1 reactivity of, 674-678

Carbonylation, of alkylboranes, 724-726 of methanol, 1520

Carbowax, 662

Carboxylate anions, IUPAC rules of nomenclature for, 195

Carboxylic acids, from acetoacetic ester acid synthesis, 854

acid-base equilibria of, 4 1

acyl chlorides from, with phosphorus chlorides, 809

with thionyl chloride, 809 acyl halides from, 857

acyl phosphate derivatives of, in biochemical esterifications, 636-637

from acyltetracarbonylferrates, 1516

from acylzirconocenes by oxidation, 1514 from alcohol oxidations, 639, 643, 855 alcohols from, by hydride reduction, 610,

809-8 11

aldehydes from, by hydride reduction, 719, 810-81 1

from aldehydes, Baeyer-Villiger, 713-7 14 Cannizzaro, 707-709

with oxidizing agents, 855 oxygen, 712-7 13 permanganate, 712

silver oxide, 712 from 2-alkanones, 855

alkene additions of, 379, 808 from alkene oxidations, 855 amides from, 858, 1177-1 178 from amides, 854

anhydrides from, 771, 857

from Arndt-Eistert synthesis, 855, 1200 biosynthesis of, 1480-1482

borane reduction of, 707-708

bromination of, Hell-Volhard-Zelinsky reaction and, 814-815

from Cannizzaro reaction, 855 carboxylic esters from, 856

chiral, as resolving agents, 867-869 chlorination of, 815

decarboxylation of, carboxylate radicals and, 812-813

electrolytic, 813

with lead tetraethanoate, 814 with mercuric oxide, 814

silver salts and bromine, 813-814 thermal, 811-8 12

Index

with diazomethane, 1199

from dicarboxylic acid decarboxylations, 847 dimers of, 791

electronic spectra of (table), 793, 795 esterification of, with alkenes, 808

mechanism and practice of, 615-6 18, 807-808 side reactions in, 807-808

steric hindrance and, 807-808 from esters, 854

as fatty acids, 789-791

functional derivatives of (table), 817-820 general characteristics of, 788-791 general reactions of, 796

a-halo, nucleophilic reactivity of, 815-8 17 synthetic uses of, 815-8 17

P-halo, from unsaturated acids, 841-842 from haloform reaction, 855

halogenation of, Hell-Volhard-Zelinsky reaction and, 814-8 15

hydrogen bonding of, 791 hydroxy, dehydration of, 843

lactones from, 843 synthesis of, 835-836 thermal reactions of, 843

from unsaturated acids, 841-842 infrared frequencies, 276-277, 680 infrared spectra of, 28 1-282, 793-794 ionization of, constants for (table), 792

electrostatic interpretation of, 799-800 entropy and, 801-802

inductive effects and, 798-800 relative to other acids, 789, 796-797 resonance and 796-798

solvation effects on, 801-802 substituent effects on, 798-802

IUPAC rules of nomenclature for, 195

from ketones, by Baeyer-Villiger oxidation, 855 by Favorskii rearrangement, 748-749

by haloform reaction, 746-747

by Kolbe-Schmitt reaction, 1298-1299 from malonic ester acid synthesis, 854 metabolism of, 837-840

from nitriles, 854 nmr spectra of, 793

nucleophilic attack on, 805-806 from organometallics, 854

from oxidation of alkyl aryl ketones, 1317 from oxidation of alkylarenes, 1317

from 3-oxobutanoic esters, 834, 854 from ozonides and methanol, 432 from phenols, 1298-1299

physical properties of (table), 791-792 preparation of (table), 854-855

from propanedioate esters, 834, 854 protecting groups for (table), 12361239 protonation of, 617

radical-chain addition to alkenes and alkynes, 389

reduction of, to aldehydes, 810-8 11 with diborane, 810-8 11

with metal hydrides, 809-8 10 resolution of chiral forms of, 866-867

with sulfur tetrafluoride, 705 trifluoromethyl derivatives from, 1318 unsaturated, 1,4-additions to, 840-841

in [4+21 cycloadditions (table), 493-494 hydration of, 841-842

hydrogen bromide addition to, 841-842 lactones from, 842-843

rearrangement of, 841 synthesis of, 836

Carboxylic anhydrides, acylation of arenes with, 1051, 1054

alcohols from, with Grignard reagents, 609 by hydride reduction, 824-825

amides from, 858, 1121-1 122, 1177-1 178 with amino acids, 1222

carboxylic esters from, 615-616, 856 from carboxylic acids, with ketene, 771 from dicarboxylic acids, 847 esterification of, 615-618, 856

as functional derivatives of carboxylic acids, 818 hydrolysis of, 820

infrared frequencies, 680

as intermediates in enzyme-induced reactions, 12631265

IUPAC rules of nomenclature for, 198 preparation of (table), 557, 857 unsaturated, in [4+21 cycloadditions (table),

493-494

Carboxylic esters, acidities of (table), 736-738 from acids with diazomethane, 1199

acyl halides from, 857 acyloin reaction of, 852-853 from acylzirconocenes, 1514

from alcohols and acyl halides, 616-617, 856 from alcohols and anhydrides, 616-617, 856 from alcohols and carboxylic acids, 615-6 18,

806-808, 856 alcohols and ketene, 771

alcohols from, with Grignard reagents, 609 by hydride reduction, 824-825

sodium and alcohol reduction, 825

from alcohols, thionyl chloride and carboxylate salts, 855

aldol additions of, 835

from alkyl halides and carboxylate salts, 856 amides from, 858, 1121-1 122, 1177-1 178

m i n e s from, by Curtius degradation, 1150 biochemical formation of, phosphate esters

and, 635-637 carboxylic acids from, 854

from carboxylic acids, with alcohols, 615-618, 806-808, 856

with alkenes, 808

with diazomethane, 856, 1199 Claisen condensation of, 829-832 enolate anions from, 835-836

by ester interchange, 856

as functional derivatives of carboxylic acids, 818 from Grignard reagents (table), 579, 583

with Grignard reagents, 823-824 hydrazides from, 858 a-hydrogen acidity, 737, 825-826

hydrolysis of, 820-82 1

Harnmett correlation of, 1329-1330, 1334, 1336

hydroxaniic acids from, 858 hydroxy, synthesis of, 835-836

unsaturated esters from, 836 infrared frequencies, 680 interchange reaction of, 821

IUPAC rules of nomenclature for, 197-198 from ketones, Baeyer-Villiger, 713-7 14

by Favorskii rearrangement, 748-749 mechanism of formation of, 615-6 18 from nitriles, 856

preparation of (table), 856

as protecting groups for OH, 652 reactivity correlation of, 13291330 soaps from hydrolysis of, 790 unsaturated, 1,4-additions to, 844-845

in /4+23 cycloadditions (table), 493-494 cycloadditions with diazomethane, 1200 Michael addition of, 844-845 rearrangement of, 841

synthesis of, 836

Carboxypeptidase, mechanism of action of, 12621265

in peptide sequencing, 1231 precursor of, 1269 properties, 1250

proteolytic properties of, 1260 Carcinogens, aflatoxins as, 1163

amines as, 1161-1162 arenes as, 1026

azo compounds as, 1162 chloroethene as, 549

N-nitroso compounds as, 11631164 Cardiac poison, 1473

P-Carotene, electronic absorptions of, 1401 with singlet oxygen, 1393

structure of, 33

as vitamin A precursoi; 1469 Carotenes, biosynthesis of, 1485, 1488 Carvone, structure and odor, 140 CaryophyIlene, 1464

Catalysis (see also Acid catalysis, Base catalysis, etc.)

of alkene hydrogenation, heterogeneous metals and, 410-414

homogeneous metal complexes and, 417-4 18, 1517-1521

mechanisms for, alkene metathesis, 1520-1 521 1,3-butadiene trimerization, 1523 homogeneous hydrogenation with rhodium,

1517-1518 hydroformylation, 1518-15 19

of methanol carbonylation, 1520 methylpropandioyl to butanedioyl coenzyme

A, 1526

of 0x0 reaction, 1518-1519 Catalyst, definition of, 16 Catalytic re-forming, 10791080 Catechol (see 1,2-Benzenediol)

Cationic polymerization, of alkenes, 393-395

lndex

Cedar, oil of, 1498 Cedrene, synthesis of, 1498 Celery, oil of, 1464

Cellobiose, from cellulose, 933 structure and configuration of, 929

Cellosolves, 656

Celluloid, 933

Cellulose, biological degradation of, 934 derivatives, 933

enzyme induced hydrolysis, 1270 hydrolysis of, 933-934, 1270 properties and occurrence of, 908 structure of, 932-933

uses of, 933 Cellulose acetate, 933

Cellulose acetate butyrate, 933 Cellulose xanthate, 933 Cephalosporins, biosynthesis of, 1492

structure and function of, 1491 synthesis of, 1492

Cercropia moth hormones, 1469 Ceric ion, oxidation of

cyclobutadieneirontricarbonyl with, 1507 Charge relay mechanism, in proteolytic

enzymes, 1266

Charge transfer complexes, from alkenes and halogens, 367

in arene halogenation, 10441045

of arenes and nitro compounds, 1192-1 193 electronic spectra of, 11921193 quinhydrone as, 1307

resonance and, 11921193 Chemical Abstracts, indexes for, 51 Chemical evolution, 12821284

Chemical synthesis, principles in planning of, 513-530

Chemically induced dynamic nuclear polarization, 1353-1356

Chemiluminescence, 13951399 Chenopodium, oil of, 1466 Chiral centers (see Chirality) Chiral recognition, 869

Chirality, achiral and chiral environments, 120 of allenes, 508-5 10

of amines, 1109-1110

asymmetric synthesis and, 893-894

and biological specificity, of sense of taste and smell, 140141

chiral centers, location of, 116117 compounds without chiral carbons, 508-5 11 of trans-cycloalkenes, 475-476, 511

of cycloalkylidenes, 510 D,L convention for, 131-139 definition of, 116

diastereotopic groups and, 889 enantiotopic groups and, 888-889 Fischer projection formulas for, 128-139 of hindered biphenyls, 510-5 11

meso compounds and, 135-139 optical rotation and, 865-866 prochirality and, 888-889

R,S convention for, 879-884